JPH05205777A - Macromolecular solid electrolyte battery - Google Patents
Macromolecular solid electrolyte batteryInfo
- Publication number
- JPH05205777A JPH05205777A JP4009146A JP914692A JPH05205777A JP H05205777 A JPH05205777 A JP H05205777A JP 4009146 A JP4009146 A JP 4009146A JP 914692 A JP914692 A JP 914692A JP H05205777 A JPH05205777 A JP H05205777A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- material layer
- electrode active
- negative electrode
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高分子固体電解質電池に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer solid electrolyte battery.
【０００２】[0002]
【従来の技術】近年、固体の電解質を用いた電気化学セ
ル（固体電解質電池）の開発が盛んに行われている。2. Description of the Related Art Recently, an electrochemical cell (solid electrolyte battery) using a solid electrolyte has been actively developed.
【０００３】固体電解質電池に用いる固体電解質には、
無機物質を用いる固体電解質と、高分子化合物を用いる
固体電解質とがある。無機物質を用いる固体電解質はＬ
ｉ4ＳｉＯ4 −Ｌｉ3 ＰＯ4 ，Ｌｉ2 Ｓ−ＬｉＩ−Ｂ2
Ｓ3 （キャリアイオンはＬｉ＋）及びＲｂＣｕＩ1.5 Ｃ
ｌ3.5 （キャリアイオンはＣｕ＋）等の無機物質を電解
質材料として用いている。高分子化合物を用いる固体電
解質はポリエチレンオキサイド（ＰＥＯ）及びポリプロ
ピレンオキサイド（ＰＰＯ）等のポリエーテル類［Ｌｉ
＋をキャリアイオンとすると伝導度は１０-5〜１０-4Ｓ
／cm（室温）］からなる高分子化合物を電解質材料とし
て用いている。Solid electrolytes used in solid electrolyte batteries include
There are solid electrolytes using inorganic substances and solid electrolytes using polymer compounds. The solid electrolyte using an inorganic substance is L
i 4 SiO 4 -Li 3 PO 4 , Li 2 S-LiI-B 2
S 3 (carrier ion is Li + ) and RbCuI 1.5 C
An inorganic substance such as l 3.5 (carrier ion is Cu + ) is used as an electrolyte material. Solid electrolytes using polymer compounds include polyethers such as polyethylene oxide (PEO) and polypropylene oxide (PPO) [Li
When + is a carrier ion, the conductivity is 10 -5 to 10 -4 S
/ Cm (room temperature)] is used as an electrolyte material.
【０００４】無機物質を用いる固体電解質は硬くてもろ
いため、電解質を薄膜にすることが困難である。これに
対して高分子化合物を用いる固体電解質は、電解質の表
面積を広くしても電解質を薄膜化しやすい。しかも高分
子化合物は柔軟性があるため電解質と活物質との密着性
がよい。このように無機物質に比べて高分子化合物の方
が固体電解質の材料として適しており、現在では高分子
化合物を用いる固体電解質（高分子固体電解質電池）の
研究が盛んに行われている。Since a solid electrolyte using an inorganic substance is hard and brittle, it is difficult to form the electrolyte into a thin film. On the other hand, a solid electrolyte using a polymer compound is likely to have a thin electrolyte even if the surface area of the electrolyte is increased. Moreover, since the polymer compound is flexible, the adhesion between the electrolyte and the active material is good. As described above, a polymer compound is more suitable as a material for a solid electrolyte than an inorganic substance, and at present, a solid electrolyte (polymer solid electrolyte battery) using a polymer compound is actively researched.
【０００５】一般に高分子固体電解質電池はイオン伝導
度が低くしかも薄膜化が容易であるため、正極活物質層
と負極活物質層とが高分子固体電解質を介してシート状
に積層されて構成されている。In general, a polymer solid electrolyte battery has a low ionic conductivity and can be easily formed into a thin film. Therefore, a positive electrode active material layer and a negative electrode active material layer are laminated in a sheet form via a polymer solid electrolyte. ing.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、高分子
固体電解質を作成するために用いるジメキシエタン（Ｄ
ＭＥ）等の有機溶液には微量の水分または不純物が含ま
れている。また重合等で作成したポリエーテル類等の電
解質材料にも未反応物が不純物として残留している。こ
れら不純物は電池の製造工程において有機溶剤を蒸発す
る際に、そのほとんどは有機溶剤と一緒に除去される。
しかしながら、有機溶剤を完全に蒸発しても、不純物を
完全に除去することはできず、その一部は電解質中に残
留してしまう。そして、高分子固体電解質中に残留した
不純物は、活物質層と反応してガスを発生し、高分子固
体電解質と活物質層との間にガス溜りを形成する。この
ようなガス溜りが形成されると、電池の内部抵抗が高く
なるという問題が発生する。また、電池の製造工程にお
いて活物質層を電解質に密着させる際にも電解質中に残
留した不純物が活物質層と反応してガスを発生し、この
ガスが電解質と活物質層との間に残ると、内部抵抗の高
い電池が製造されるという問題が発生する。またこのよ
うなガス溜りができると、電極の一部分（ガス溜りを間
に有しないで電解質と負極活物質層が密着した部分）に
電極反応が集中するため電池寿命が短くなるという問題
もあった。However, the dimexiethane (D) used for preparing the polymer solid electrolyte is
A small amount of water or impurities is contained in an organic solution such as ME). In addition, unreacted substances remain as impurities in electrolyte materials such as polyethers formed by polymerization and the like. Most of these impurities are removed together with the organic solvent when the organic solvent is evaporated in the battery manufacturing process.
However, even if the organic solvent is completely evaporated, the impurities cannot be completely removed, and some of them remain in the electrolyte. Then, the impurities remaining in the solid polymer electrolyte react with the active material layer to generate gas, and form a gas pool between the solid polymer electrolyte and the active material layer. When such a gas pool is formed, the internal resistance of the battery becomes high. Further, even when the active material layer is brought into close contact with the electrolyte in the battery manufacturing process, impurities remaining in the electrolyte react with the active material layer to generate a gas, and the gas remains between the electrolyte and the active material layer. Then, there arises a problem that a battery having a high internal resistance is manufactured. Further, when such a gas pool is formed, the electrode reaction concentrates on a part of the electrode (the part where the electrolyte and the negative electrode active material layer are in close contact without having the gas pool in between), which shortens the battery life. ..
【０００７】本発明の目的は上記課題を解決して、内部
抵抗が小さく寿命の長い高分子固体電解質電池を提供す
ることにある。An object of the present invention is to solve the above problems and to provide a polymer solid electrolyte battery having a small internal resistance and a long life.
【０００８】[0008]
【課題を解決するための手段】請求項１の発明は、正極
活物質層と負極活物質層とが高分子固体電解質を介して
積層されている高分子固体電解質電池を対象として、正
極活物質層及び負極活物質層の少なくとも一方の層がガ
ス通気性を有している。The invention of claim 1 is directed to a solid polymer electrolyte battery in which a positive electrode active material layer and a negative electrode active material layer are laminated via a solid polymer electrolyte, and a positive electrode active material. At least one of the layer and the negative electrode active material layer has gas permeability.
【０００９】請求項２の発明は、負極活物質層全体にガ
ス通気孔を分散して形成する。According to the second aspect of the present invention, gas vent holes are formed dispersed throughout the negative electrode active material layer.
【００１０】[0010]
【作用】請求項１の発明のように、活物質層にガス通気
性を持たせると、高分子固体電解質中に残存する不純物
が活物質層と反応して発生するガスは、活物質層のガス
通気性により、電解質層と活物質層との間から外に放出
される。そのため、高分子固体電解質と活物質層との間
に実質的にガス溜りが形成されることがなく、電池の内
部抵抗の増加を防止できる。When the active material layer is made gas permeable as in the invention of claim 1, the gas generated by the reaction of impurities remaining in the solid polymer electrolyte with the active material layer is generated in the active material layer. Due to the gas permeability, the gas is released outside between the electrolyte layer and the active material layer. Therefore, a gas pool is not substantially formed between the polymer solid electrolyte and the active material layer, and an increase in internal resistance of the battery can be prevented.
【００１１】請求項２の発明のように、負極活物質層全
体にガス通気孔を分散して形成することにより、ガス通
気性を負極活物質層に付与すると、ガス溜りの発生を全
体的に阻止できる上、ガス通気孔の中に高分子固体電解
質の一部が入ることにより、負極活物質層と高分子固体
電解質との接触面積が増大するため、電池の充放電特性
が向上する。また、電池の充放電によりリチウムイオン
の出入りが生じて正極活物質が体積変化を起こしても、
ガス通気孔中に弾性を有する高分子固体電解質が更に入
ることにより、正極活物質中の体積膨脹を吸収するので
電池全体の膨脹収縮を緩和できる。When gas permeation is imparted to the negative electrode active material layer by forming gas vent holes dispersed throughout the negative electrode active material layer as in the second aspect of the present invention, generation of a gas pool is entirely generated. In addition, the contact area between the negative electrode active material layer and the solid polymer electrolyte is increased due to the part of the solid polymer electrolyte entering the gas vent hole, which improves the charge / discharge characteristics of the battery. In addition, even if the positive and negative electrode active material undergoes volume change due to the inflow and outflow of lithium ions due to charge and discharge of the battery,
When the solid polymer electrolyte having elasticity is further introduced into the gas vent hole, the expansion of volume of the positive electrode active material is absorbed, so that the expansion and contraction of the entire battery can be relaxed.
【００１２】[0012]
【実施例】以下、本発明の実施例を図面を参照して詳細
に説明する。Embodiments of the present invention will now be described in detail with reference to the drawings.
【００１３】図１は本発明の一実施例の高分子固体電解
質電池を切断したものの斜視図である。図１において、
１は正極であり、この正極１はステンレス箔からなる正
極集電体２と、該集電体２の一方の表面２ａ上に配置さ
れたバナジン酸（Ｖ2 Ｏ5 ・ｎＨ2 Ｏ）からなる正極活
物質層３とから構成されている。この正極活物質層３
は、集電体２の表面２ａに対して外周端部２ｂを残すよ
うにして配置されている。４は負極であり、この負極４
はステンレス箔からなる負極集電体５と、該集電体５の
一方の表面５ａ上に配置されたリチウム（Ｌｉ）箔から
なる負極活物質層６とから構成されている。この負極活
物質層６は、集電体５の表面５ａに対して外周端部５ｂ
を残すようにして配置されている。本実施例の電池では
負極活物質層６を形成するＬｉ箔にガス通気孔６ａが分
散して形成されている［図２（ｂ）参照］。尚、正極集
電体２及び負極集電体５は、それぞれ電池の外装ケース
の一部を構成し且つ端子の機能を果たしている。７は高
分子固体電解質であり、この高分子固体電解質７に正極
活物質層３と負極活物質層６とを接触させるようにして
正極１と負極４と高分子固体電解質７とが積層されてい
る。この実施例では、高分子固体電解質７はメトキシオ
リゴエチレンオキシポリホスファゼン（ＭＥＰ７）と過
塩素酸リチウム（ＬｉＣｌＯ4 ）との混合物により形成
されている。８は加熱されると表面から溶融して接着性
を示す枠部材としてのホットメルトである。このホット
メルト８は集電体２または５の外周端部２ｂまたは５ｂ
に対応した輪郭が矩形状を呈するリングであり、具体的
にはポリオレフィン系樹脂から形成されている。集電体
２及び５の外周端部２ｂ及び５ｂがホットメルト８に接
続されて電池が組み立てられている。FIG. 1 is a perspective view of a cut polymer solid electrolyte battery of one embodiment of the present invention. In FIG.
Reference numeral 1 is a positive electrode, and the positive electrode 1 is composed of a positive electrode current collector 2 made of stainless steel foil, and vanadic acid (V 2 O 5 .nH 2 O) arranged on one surface 2 a of the current collector 2. It is composed of the positive electrode active material layer 3. This positive electrode active material layer 3
Are arranged so that the outer peripheral end 2b is left with respect to the surface 2a of the current collector 2. 4 is a negative electrode, and this negative electrode 4
Is composed of a negative electrode current collector 5 made of a stainless foil and a negative electrode active material layer 6 made of a lithium (Li) foil arranged on one surface 5a of the current collector 5. The negative electrode active material layer 6 has an outer peripheral end 5b with respect to the surface 5a of the current collector 5.
It is arranged so as to leave. In the battery of this example, the gas vent holes 6a are formed dispersedly in the Li foil forming the negative electrode active material layer 6 [see FIG. 2 (b)]. The positive electrode current collector 2 and the negative electrode current collector 5 each form a part of the outer case of the battery and also function as terminals. 7 is a solid polymer electrolyte, and the positive electrode 1, the negative electrode 4, and the solid polymer electrolyte 7 are laminated so that the positive electrode active material layer 3 and the negative electrode active material layer 6 are brought into contact with the solid polymer electrolyte 7. There is. In this example, the solid polymer electrolyte 7 is formed of a mixture of methoxyoligoethyleneoxypolyphosphazene (MEP7) and lithium perchlorate (LiClO 4 ). Reference numeral 8 is a hot melt as a frame member that melts from the surface when heated and exhibits adhesiveness. This hot melt 8 is the outer peripheral end 2b or 5b of the current collector 2 or 5.
Is a ring having a rectangular outline corresponding to, and is specifically formed of a polyolefin resin. The outer peripheral ends 2b and 5b of the current collectors 2 and 5 are connected to the hot melt 8 to assemble the battery.
【００１４】次にこの実施例の高分子固体電解質電池を
製造する方法を具体的に説明する。まずアモルファスの
Ｖ2 Ｏ5 を２〜３重量％の割合で蒸留水に溶かした溶液
を４５×４５×０．０２mmのステンレス箔からなる正極
集電体２の一方の表面２ａの中央部分に３５×３５mmの
大きさで塗布した。これを常温で乾燥させた後、さらに
比較的高温で乾燥させて、正極集電体２の表面２ａに厚
み１０μm のＶ2 Ｏ5・ｎＨ2 Ｏの正極活物質層３を有
する正極１を作った。次に図２（ａ）に示すように厚み
４０μm のＬｉ箔のロール９を３５×３５mmの寸法に切
断して負極活物質用Ｌｉ箔を作り、この負極活物質用Ｌ
ｉ箔に図２（ｂ）に示すように径０．０１〜０．０３mm
のガス通気孔６ａをＬｉ箔全体に分散するようにあけ、
メッシュ状のＬｉ箔からなる負極活物質層６を得た。ち
なみに、負極活物質層６の表面積に対するガス通気孔６
ａの総面積は８０％〜９０％とするのが好ましい。次に
１００重量％のＭＥＰ７と６重量％のＬｉＣｌＯ4 とを
ＤＭＥ中に溶かした高分子固体電解質用溶液を正極１の
正極活物質層３全体を覆うように３７×３７mmの大きさ
で正極１上に塗布した。これを１時間程度常温で乾燥さ
せて半乾燥電解質を作った。乾燥中に電解質用溶液から
水分と一緒にＤＭＥの大部分は除去される。次に半乾燥
電解質の上にＬｉ箔からなる負極活物質層６を載置し、
正極集電体２の外周端部２ｂの上にホットメルト８を載
置した。そして、負極活物質層６とホットメルト８とを
覆うようにして正極集電体２と同寸法同材質の負極集電
体５を載置した。次にホットメルト８を集電体２及び５
の外周端部２ｂ及び５ｂに数箇所溶着させた後、真空乾
燥を約１日行なった。この真空乾燥により電解質中にわ
ずかに残っているＤＭＥや水分またはポリホスファゼン
の未反応の低分子物を電解質から略完全に除去して高分
子固体電解質７を得た。その後、集電体２及び５の外周
端部２ｂ及び５ｂにホットメルト８を完全に溶着して高
分子固体電解質電池を製造した。Next, a method for manufacturing the polymer solid electrolyte battery of this embodiment will be specifically described. First, a solution prepared by dissolving amorphous V 2 O 5 in distilled water in a proportion of 2 to 3% by weight was applied to the central portion of one surface 2 a of the positive electrode current collector 2 made of stainless steel foil of 45 × 45 × 0.02 mm. It was applied in a size of × 35 mm. This is dried at room temperature and then at a relatively high temperature to form a positive electrode 1 having a positive electrode active material layer 3 of V 2 O 5 .nH 2 O having a thickness of 10 μm on the surface 2a of the positive electrode current collector 2. It was Next, as shown in FIG. 2A, a roll 9 of Li foil having a thickness of 40 μm is cut into a size of 35 × 35 mm to prepare a Li foil for negative electrode active material.
As shown in Fig. 2 (b), the i foil has a diameter of 0.01 to 0.03 mm.
The gas vents 6a of 6 are opened so as to be dispersed over the entire Li foil,
A negative electrode active material layer 6 made of a mesh Li foil was obtained. Incidentally, the gas vent holes 6 with respect to the surface area of the negative electrode active material layer 6
The total area of a is preferably 80% to 90%. Next, a solution for polymer solid electrolyte in which 100 wt% of MEP7 and 6 wt% of LiClO 4 were dissolved in DME was applied to the positive electrode 1 in a size of 37 × 37 mm so as to cover the entire positive electrode active material layer 3 of the positive electrode 1. Applied on top. This was dried at room temperature for about 1 hour to prepare a semi-dry electrolyte. Most of the DME along with water is removed from the electrolyte solution during drying. Next, the negative electrode active material layer 6 made of Li foil was placed on the semi-dry electrolyte,
The hot melt 8 was placed on the outer peripheral end 2 b of the positive electrode current collector 2. Then, the negative electrode current collector 5 having the same size and the same material as the positive electrode current collector 2 was placed so as to cover the negative electrode active material layer 6 and the hot melt 8. Next, the hot melt 8 is added to the current collectors 2 and 5
After being welded to the outer peripheral ends 2b and 5b at several points, vacuum drying was performed for about 1 day. By this vacuum drying, DME, water, or unreacted low-molecular substances such as polyphosphazene slightly remaining in the electrolyte were almost completely removed from the electrolyte to obtain a polymer solid electrolyte 7. Then, the hot melt 8 was completely welded to the outer peripheral end portions 2b and 5b of the current collectors 2 and 5 to manufacture a polymer solid electrolyte battery.
【００１５】本実施例では電池を製造する際に、半乾燥
電解質上にＬｉ箔（負極活物質層６）を載置するため、
半乾燥電解質中の不純物が負極活物質層６と反応して水
素ガスが発生する。しかしながら、水素ガスはガス通気
孔６ａを通って、半乾燥電解質と負極活物質層６との間
から放出される。また、電池を密封した後に高分子固体
電解質７に残存している不純物と負極活物質層６とが反
応して水素ガスが発生しても、水素ガスはガス通気孔６
ａを通った後、負極活物質層６と負極集電体５との間及
び負極集電体５とホットメルト８との間のわずかな空隙
部を通って電池外に放出される。In this embodiment, since the Li foil (negative electrode active material layer 6) is placed on the semi-dried electrolyte when the battery is manufactured,
Impurities in the semi-dry electrolyte react with the negative electrode active material layer 6 to generate hydrogen gas. However, hydrogen gas is released from between the semi-dry electrolyte and the negative electrode active material layer 6 through the gas vent holes 6a. In addition, even if impurities remaining in the solid polymer electrolyte 7 react with the negative electrode active material layer 6 after the battery is sealed to generate hydrogen gas, the hydrogen gas is discharged through the gas vent holes 6.
After passing through a, it is discharged to the outside of the battery through a slight gap between the negative electrode active material layer 6 and the negative electrode current collector 5 and between the negative electrode current collector 5 and the hot melt 8.
【００１６】次に本発明の実施例の電池の特性を調べる
ために試験を行った。まず本発明の実施例の電池と、負
極活物質層にガス通気孔を形成しない従来の電池とを各
々１０個製造した。尚、従来の電池は、負極活物質層に
ガス通気孔が形成されていないこと以外は本発明の実施
例の電池と同じ構造を有している。各電池の放電容量
は、２５μA/cm2 ，終了電圧２．０Ｖ，２５℃の放電条
件で測定した。表１は測定結果を示している。Next, a test was conducted to examine the characteristics of the battery of the example of the present invention. First, 10 batteries were manufactured for each of the battery of the example of the present invention and a conventional battery in which a gas vent was not formed in the negative electrode active material layer. The conventional battery has the same structure as the battery of the embodiment of the present invention except that the gas vent is not formed in the negative electrode active material layer. The discharge capacity of each battery was measured under the discharge conditions of 25 μA / cm 2 , final voltage of 2.0 V, and 25 ° C. Table 1 shows the measurement results.
【００１７】[0017]
【表１】 この測定結果から本発明の実施例の電池では、負極活物
質層６と高分子固体電解質７との間にガス溜りが実質的
に存在しないため、負極活物質層６と高分子固体電解質
７と間の密着性が良くなって内部抵抗が小さくなり、そ
の結果、従来の電池に比べて放電容量のバラツキが小さ
く、しかも放電容量の平均値が高くなるのが判る。[Table 1] From the measurement results, in the battery of the example of the present invention, since there was substantially no gas pool between the negative electrode active material layer 6 and the solid polymer electrolyte 7, the negative electrode active material layer 6 and the solid polymer electrolyte 7 were It can be seen that the adhesion between the two is improved and the internal resistance is reduced, resulting in less variation in discharge capacity and higher average discharge capacity than in conventional batteries.
【００１８】次に本発明の実施例の電池と従来の電池と
を用いて以下の条件で充放電を繰り返してサイクル特性
を測定した。Next, using the battery of the example of the present invention and the conventional battery, charging and discharging were repeated under the following conditions to measure cycle characteristics.
【００１９】 測定温度：２５℃ 充電条件：電流密度 ２５μA/cm3 、４．２Ｖカット 放電条件：電流密度 ２５μA/cm3 、終止電圧 ２Ｖ 図３は測定結果を示した表である。本図において、曲線
Ａは本発明の実施例の電池の特性曲線を示し、曲線Ｂは
従来の電池の特性曲線を示している。図３より本発明の
実施例の電池のサイクル特性が従来の電池のサイクル特
性より高いのが判る。Measurement temperature: 25 ° C. Charge condition: Current density 25 μA / cm 3 , 4.2 V cut Discharge condition: Current density 25 μA / cm 3 , Final voltage 2 V FIG. 3 is a table showing the measurement results. In the figure, a curve A shows the characteristic curve of the battery of the example of the present invention, and a curve B shows the characteristic curve of the conventional battery. It can be seen from FIG. 3 that the cycle characteristics of the battery of the embodiment of the present invention are higher than the cycle characteristics of the conventional battery.
【００２０】尚、本実施例の電池ではＬｉ箔にパンチン
グ等によりガス通気孔を分散して形成した負極活物質層
を用いたが、Ｌｉ線等により形成した導電性不織布に活
物質を保持させて形成した負極活物質層や、Ｌｉ箔等を
エキスパンダ状に加工して形成した負極活物質層を用い
ても構わない。In the battery of this embodiment, a negative electrode active material layer formed by dispersing gas vent holes in a Li foil by punching or the like was used. However, the conductive material is held in a conductive non-woven fabric formed of Li wire or the like. The negative electrode active material layer formed by the above process or the negative electrode active material layer formed by processing Li foil or the like into an expander shape may be used.
【００２１】上記実施例では、負極活物質層６だけにガ
ス通気性を付与している。しかしながら、高分子固体電
解質７に残存する不純物と正極活物質層３とが反応する
と僅かであるが、一酸化炭素または二酸化炭素等のガス
が発生する。したがって、正極活物質層と正極集電体と
の間にもガス溜りが発生する可能性がある。しかしなが
ら、このガス溜りはガス通気性を有しない負極活物質層
と高分子固体電解質との間に発生するガス溜りと比べれ
ば僅かなものであり内部抵抗への影響は少ない。したが
って、実用的な見地から見た場合には、正極活物質に積
極的にガス通気性を持たせることは必要ない。尚、正極
活物質層にガス通気性を付与する場合には、上記実施例
と同様に、正極活物質層の層全体にガス通気孔を分散し
て形成すればよい。また、カーボン繊維等からなる導電
性不織布に正極活物質を保持させてガス通気性を有する
正極活物質層を形成してもよい。In the above embodiment, gas permeability is imparted only to the negative electrode active material layer 6. However, when impurities remaining in the solid polymer electrolyte 7 and the positive electrode active material layer 3 react with each other, a gas such as carbon monoxide or carbon dioxide is slightly generated. Therefore, gas accumulation may occur between the positive electrode active material layer and the positive electrode current collector. However, this gas pool is slight compared with the gas pool generated between the negative electrode active material layer having no gas permeability and the solid polymer electrolyte, and has little influence on the internal resistance. Therefore, from a practical point of view, it is not necessary that the positive electrode active material be positively gas permeable. When the positive electrode active material layer is provided with gas permeability, gas vent holes may be dispersed throughout the layer of the positive electrode active material layer as in the above-described embodiment. Alternatively, a positive electrode active material layer having gas permeability may be formed by holding a positive electrode active material on a conductive non-woven fabric made of carbon fiber or the like.
【００２２】また本実施例の電池は正極活物質層として
Ｖ2 Ｏ5 ・ｎＨ2 Ｏを用い、負極活物質層としてＬｉを
用いているが、他の材質からなる活物質層を用いる高分
子固体電解質電池にも本発明を適応できるのは勿論であ
る。In the battery of this embodiment, V 2 O 5 .nH 2 O is used as the positive electrode active material layer and Li is used as the negative electrode active material layer, but a polymer using an active material layer made of another material is used. Of course, the present invention can be applied to a solid electrolyte battery.
【００２３】[0023]
【発明の効果】請求項１の発明によれば、活物質層がガ
ス通気性を有しているため、高分子固体電解質と活物質
層との間にガス溜りが形成されず、電池の内部抵抗を低
くできる。そのため寿命の長い高分子固体電解質電池を
提供できる。According to the first aspect of the present invention, since the active material layer has gas permeability, no gas reservoir is formed between the solid polymer electrolyte and the active material layer, and the inside of the battery is The resistance can be lowered. Therefore, a polymer solid electrolyte battery having a long life can be provided.
【００２４】請求項２の発明によれば、負極活物質層全
体にガス通気孔が分散して形成されているため、ガス溜
りの発生を負極活物質層全体で阻止できる。また、負極
活物質層と高分子固体電解質との接触面積が増大するた
め、電池の充放電特性が向上する。また、電池の充放電
により正極活物質が体積変化を起こしても、ガス通気孔
中に弾性を有する高分子固体電解質が更に入ることによ
り電池全体の膨脹収縮を緩和でき、電池の長寿命化が図
れる。According to the second aspect of the present invention, since the gas vent holes are formed dispersedly in the entire negative electrode active material layer, generation of a gas pool can be prevented in the entire negative electrode active material layer. Moreover, since the contact area between the negative electrode active material layer and the solid polymer electrolyte is increased, the charge / discharge characteristics of the battery are improved. Further, even if the positive electrode active material undergoes a volume change due to charge / discharge of the battery, expansion and contraction of the entire battery can be relaxed by further inclusion of the elastic polymer solid electrolyte in the gas vent hole, which prolongs the life of the battery. Can be achieved.
【図１】本発明の実施例の高分子固体電解質電池を切断
したものの斜視図である。FIG. 1 is a perspective view of a cut polymer solid electrolyte battery of an example of the present invention.
【図２】（ａ）及び（ｂ）は、本発明の実施例の高分子
固体電解質電池に用いる負極活物質層を製造する過程を
示す図である。2A and 2B are diagrams showing a process of producing a negative electrode active material layer used in a polymer solid electrolyte battery of an example of the present invention.
【図３】試験に用いた電池のサイクル特性を示す図であ
る。FIG. 3 is a diagram showing cycle characteristics of a battery used in a test.
３…正極活物質層、６…負極活物質層、６ａ…ガス通気
孔、７…高分子固体電解質。3 ... Positive electrode active material layer, 6 ... Negative electrode active material layer, 6a ... Gas vent, 7 ... Polymer solid electrolyte.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 弘中 健介 東京都新宿区西新宿二丁目１番１号 新神 戸電機株式会社内 (72)発明者 早川 他▲く▼美 東京都新宿区西新宿二丁目１番１号 新神 戸電機株式会社内 (72)発明者 小牧 昭夫 東京都新宿区西新宿二丁目１番１号 新神 戸電機株式会社内 (72)発明者 中長 偉文 徳島県徳島市川内町加賀須野463番地 大 塚化学株式会社徳島研究所内 (72)発明者 谷口 正俊 徳島県徳島市川内町加賀須野463番地 大 塚化学株式会社徳島研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kensuke Hironaka, Kensuke Hironaka, 2-1-1, Nishishinjuku, Shinjuku-ku, Tokyo Within Shinjin Todenki Co., Ltd. (72) Inventor, Hayakawa, etc. 2-1-1 Shinshin-Toden Electric Co., Ltd. (72) Inventor Akio Komaki 2-1-1-1 Nishishinjuku, Shinjuku-ku, Tokyo Shinjin-Toden Electric Co., Ltd. (72) Inventor, Weibun Tokushima Prefecture 463 Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Laboratory, Otsuka Chemical Co., Ltd. (72) Masatoshi Taniguchi 463, Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture, Tokushima Laboratory, Otsuka Chemical Co., Ltd.
Claims (2)
体電解質を介して積層されている高分子固体電解質電池
において、 前記正極活物質層及び負極活物質層の少なくとも一方の
層がガス通気性を有していることを特徴とする高分子固
体電解質電池。1. A solid polymer electrolyte battery in which a positive electrode active material layer and a negative electrode active material layer are laminated with a solid polymer electrolyte interposed between at least one of the positive electrode active material layer and the negative electrode active material layer. A polymer solid electrolyte battery having gas permeability.
して形成されていることを特徴とする請求項１に記載の
高分子固体電解質電池。2. The polymer solid electrolyte battery according to claim 1, wherein gas vent holes are formed dispersedly throughout the negative electrode active material layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4009146A JPH05205777A (en) | 1992-01-22 | 1992-01-22 | Macromolecular solid electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4009146A JPH05205777A (en) | 1992-01-22 | 1992-01-22 | Macromolecular solid electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05205777A true JPH05205777A (en) | 1993-08-13 |
Family
ID=11712486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4009146A Pending JPH05205777A (en) | 1992-01-22 | 1992-01-22 | Macromolecular solid electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05205777A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001052745A (en) * | 1999-08-04 | 2001-02-23 | Sony Corp | Nonaqueous gel secondary battery and its manufacture |
| JP2001068165A (en) * | 1999-08-26 | 2001-03-16 | Sony Corp | Nonaqueous system polymer secondary battery |
| JP2008308722A (en) * | 2007-06-13 | 2008-12-25 | Mitsubishi Heavy Ind Ltd | Water electrolysis cell, water electrolysis stack using the same, hydrogen production apparatus and solid polymer film water electrolytic apparatus |
| WO2020097327A3 (en) * | 2018-11-08 | 2020-07-23 | Maxwell Technologies, Inc. | Compositions and methods for energy storage devices including salts and/or foams |
-
1992
- 1992-01-22 JP JP4009146A patent/JPH05205777A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001052745A (en) * | 1999-08-04 | 2001-02-23 | Sony Corp | Nonaqueous gel secondary battery and its manufacture |
| JP2001068165A (en) * | 1999-08-26 | 2001-03-16 | Sony Corp | Nonaqueous system polymer secondary battery |
| JP4501180B2 (en) * | 1999-08-26 | 2010-07-14 | ソニー株式会社 | Non-aqueous polymer secondary battery |
| JP2008308722A (en) * | 2007-06-13 | 2008-12-25 | Mitsubishi Heavy Ind Ltd | Water electrolysis cell, water electrolysis stack using the same, hydrogen production apparatus and solid polymer film water electrolytic apparatus |
| WO2020097327A3 (en) * | 2018-11-08 | 2020-07-23 | Maxwell Technologies, Inc. | Compositions and methods for energy storage devices including salts and/or foams |
| CN113302762A (en) * | 2018-11-08 | 2021-08-24 | 麦斯韦尔技术股份有限公司 | Compositions and methods for energy storage devices comprising salt and/or foam |
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